Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/14—Metallic material, boron or silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/001—Combinations of extrusion moulding with other shaping operations
  • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
  • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
  • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
  • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/14—Organic dielectrics
  • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/10—Polymers of propylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2007/00—Flat articles, e.g. films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene
  • C08J2323/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/021—Cleaning or etching treatments
  • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
  • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/60—Other road transportation technologies with climate change mitigation effect
  • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

• the present invention relates to a biaxially oriented polypropylene film suitable for industrial use and the like, and more particularly, to a biaxially oriented polypropylene film suitable as a dielectric for capacitors having high voltage resistance that is stable even at high temperatures. .
• the biaxially oriented polypropylene film is excellent in transparency, mechanical properties, electrical properties, etc., it is used in various applications such as packaging applications, tape applications, cable wrapping and electrical applications including capacitors.
• capacitors are particularly preferably used for high voltage capacitors because of their excellent withstand voltage characteristics and low loss characteristics, not limited to DC applications and AC applications.
• Such a biaxially oriented polypropylene film needs to be appropriately roughened from the viewpoint of voltage resistance, heat resistance, productivity, and workability. Roughening is particularly important because it improves the slipperiness and oil impregnation of the film, or provides security for metal-deposited capacitors.
• security refers to a metal-deposited capacitor that uses a metal-deposited film formed on the dielectric film as an electrode. In the event of abnormal discharge, the deposited metal scatters due to discharge energy to restore insulation and prevent short-circuiting. This is a function of maintaining the function of the capacitor or preventing the destruction of the capacitor. This security is an extremely important characteristic from the viewpoint of safety.
• Such roughening methods include mechanical methods such as embossing and sand blasting, chemical methods such as chemical etching with solvents, methods for orienting sheets mixed with different polymers such as polyethylene, and ⁇ crystals.
• a method of orienting a sheet has been proposed (see Patent Document 1).
• the mechanical method and the chemical method have a problem that the roughness density is low, and the method of orienting the sheet on which the ⁇ crystals are formed has a problem that coarse protrusions are likely to occur.
• Films roughened by these methods are not sufficiently impregnated with oil between the film layers during capacitor formation, and partly unimpregnated portions are likely to be produced, and the capacitor life may be reduced.
• the method of orienting a sheet blended with a different polymer such as polyethylene there are few bubbles remaining during capacitor formation, but when the film is recycled, it may be inappropriate for use after the different polymer is recycled. There was a problem that it was inferior in recyclability.
• the biaxially oriented polypropylene film produced by any of the methods is not sufficient in terms of safety and reliability in terms of the use conditions of capacitors at high temperatures of 100 ° C. or higher under severe conditions where the potential gradient is 250 V / ⁇ m or higher. There was a problem.
• the potential gradient is obtained by dividing the voltage applied to the capacitor dielectric film by the film thickness.
• Patent Document 4 discloses a biaxially oriented polypropylene film in which the surface roughness is controlled, but it is not sufficient for controlling the film surface roughness.
• Patent Documents 4 and 5 that define the roughness of at least one side of the film surface, as a method of forming a fine rough surface, by setting the ⁇ crystal fraction of the cast raw sheet within a certain range, the element winding property And pressure resistance can be balanced.
• the manufacturing method is not capable of sufficiently controlling the roughness of both sides of the film, and the pressure resistance and heat resistance, processing required for capacitors for automotive applications, in particular, is only required for the fine roughness of the obtained film. It did not fully satisfy sex.
• the present invention provides a biaxially oriented polypropylene film that has excellent voltage resistance even in high-voltage capacitor applications and reliability that there is little change in capacitance even under high voltage and ensures workability to the capacitor. Is an issue.
• the present invention discloses the following polypropylene film.
• (1) Contains polypropylene, has a mesopentad fraction of 95% or more and less than 98%, has a thickness of 1 to 3 ⁇ m by a micrometer method, and has a heat shrinkage stress value at 140 ° C. in the width direction of 0 Biaxially oriented polypropylene film that is ⁇ 1 N / mm 2 .
• this invention discloses the following polypropylene films as a preferable aspect of the said film.
• this invention discloses the following methods as a manufacturing method of one of the said biaxially oriented polypropylenes.
• a step of melt-extruding a polypropylene resin to obtain an unstretched sheet A step of biaxially stretching the unstretched sheet to obtain a film,
• the method for producing any one of the biaxially oriented films comprising the step (I) of relaxing the film by 20 to 30%.
• the mesopentad fraction of polypropylene in the film is 95% or more and less than 98%.
• the film has a thickness of 1 to 3 ⁇ m by a micrometer method, and a heat shrinkage stress value at 140 ° C. in the width direction of 0 to 1 N / mm 2 .
• the biaxially oriented polypropylene film of the present invention preferably has a film thickness of 1 to 3 ⁇ m by a micrometer method from the viewpoint of capacitor element size and film formation stability.
• the film thickness is preferably 1.2 ⁇ m or more, and more preferably 1.5 ⁇ m or more. Moreover, 2.5 micrometers or less, Furthermore 2.3 micrometers or less are preferable. If the film is too thin, the mechanical strength, dielectric breakdown strength, and heat resistance may be inferior. On the other hand, if the film is too thick, it is difficult to form a film having a uniform thickness, and when used as a dielectric for a capacitor, the capacity per volume becomes small.
• the polypropylene contained in the film of the present invention has a mesopentad fraction of 95% or more and less than 98%. If it is 98% or more, the productivity of a thin film may be extremely lowered. In addition, the crystallinity of the film tends to be high, the plane orientation of the amorphous part is lowered, and the withstand voltage at room temperature may be lowered. If it is less than 95%, the heat resistance and particularly the reliability at high temperatures may be lowered.
• the film of the present invention has a heat shrinkage stress value at 140 ° C. in the width direction of 0 to 1 N / mm 2 . Furthermore, 0.1 N / mm 2 or more is preferable. Moreover, 0.6 N / mm ⁇ 2 > or less is preferable.
• the thermal shrinkage stress at 140 ° C. in the width direction is less than 0 N / mm 2 , the film does not actually shrink and the film thermally expands, and the end face curls during the aging process at the time of manufacturing the capacitor, and the electrical characteristics May decrease. If it exceeds 1 N / mm 2 , the end surface may be curled due to the aging temperature at the time of manufacturing the capacitor, resulting in a problem that the electrical characteristics are deteriorated or the shape of the capacitor is deformed.
• a heat shrinkage stress value at a high temperature that cannot be expressed by a conventional heat shrinkage rate is adopted as a control factor. That is, by grasping the heat shrinkage stress value in the width direction at 140 ° C. as a control target, it is possible to obtain a suitable device finish, shape maintenance by high temperature treatment, withstand voltage at high temperature, reliability, and dimensional stability. It has become possible.
• the thermal shrinkage stress value in the longitudinal direction of 140 ° C. is 0.5 N / mm 2 or more and more 0.9N / mm 2 or more. Further, it is preferable that this value 2N / mm 2 or less, further 1.6 N / mm 2 or less. If the heat shrinkage stress value in the longitudinal direction at 140 ° C. is in the above range, the winding in the longitudinal direction at the time of capacitor formation will increase the uniformity of the gap between the film layers, improve the capacitor life and reliability, and have excellent electrical characteristics A film suitable for use can be obtained.
• the sum of the heat shrinkage stress value in the longitudinal direction and the heat shrinkage stress value in the width direction at 140 ° C. is preferably 0.5 N / mm 2 or more, and more preferably 1.0 N / mm 2 or more. Further, the sum of the stress values 2.5 N / mm 2 or less, further 2.2 N / mm 2 or less.
• the sum of the heat shrinkage stress values is within the above range, the uniformity of the gap between the film layers is increased during capacitor formation, curling of the edge is suppressed, and the capacitor life and reliability are improved. Further, the contact property with the end metallicon is good, and a capacitor having excellent electrical characteristics can be obtained.
• the heat shrinkage ratio after treatment at 140 ° C. for 15 minutes is preferably 4% or more, more preferably 4.5% or more in the longitudinal direction.
• the heat shrinkage rate is preferably 7% or less, more preferably 6% or less.
• the thermal shrinkage after treatment at 140 ° C. for 15 minutes in the width direction is preferably 0 to 2%, more preferably less than 1.5%.
• the total heat shrinkage rate after treatment at 120 ° C. for 15 minutes in the longitudinal direction and the width direction is preferably 2.5% or less, more preferably 2.2% or less.
• the uniformity of the inter-film gap and dimensional stability are improved, particularly when forming a multilayer capacitor, and the capacitor life is improved.
• the contact property between the film and the end metallicon becomes good, and a film having excellent electrical characteristics can be obtained.
• the biaxially oriented polypropylene film of the present invention has an appropriately roughened film surface. This is because an appropriate rough surface maintains the uniformity of the gap between the film layers and optimizes the ease of sliding between the films or with the transport roll. Therefore, the center line average roughness (SRa) is preferably 10 nm to 40 nm. If the center line average roughness (SRa) is too large, air may easily enter between the layers when the films are laminated, leading to deterioration of the capacitor element.
• SRa centerline average surface roughness
• This value is preferably 35 nm or less, and more preferably 30 nm or less.
• the film of the present invention defined for the heat shrinkage stress value is excellent in thermal dimensional stability at high temperature, and the balance between the heat shrinkage stress value in the longitudinal direction and the width direction and the heat shrinkage rate is controlled. It has characteristic heat absorption behavior. Capacitors obtained from such biaxially oriented polypropylene films with an appropriate rough surface maintain an appropriate clearance between the film layers. There is nothing to do. As a result, the life of the capacitor can be maintained and the safety can be stably exhibited.
• SRa value is measured based on JIS B-0601 (1982). For example, it can be measured using “Non-contact 3D fine shape measuring instrument (ET-30HK)” and “3D roughness analyzer (MODEL SPA-11)” manufactured by Kosaka Laboratory. Details of measurement conditions and the like will be described later.
• the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention preferably contains 0.05 to 10% by mass of branched polypropylene (H). Furthermore, the polypropylene resin constituting the film of the present invention is preferably a mixture of linear polypropylene and the branched polypropylene (H).
• the branched polypropylene (H) has a relationship that the melt tension (MS) and the melt flow index (MFR) measured at 230 ° C. are log (MS)> ⁇ 0.56 log (MFR) +0.74.
• a branched polypropylene (H) satisfying the formula is particularly preferable.
• the melt tension measured at 230 ° C. is measured according to the melt flow index (MFR) measurement shown in JIS-K7210 (1999). Specifically, using a melt tension tester manufactured by Toyo Seiki Seisakusho Co., Ltd., the polypropylene is heated to 230 ° C., and the molten polypropylene is discharged at an extrusion speed of 15 mm / min to form a strand, and this strand is 6.4 m / min. The tension at the time of taking up at a speed is measured to obtain the melt tension (unit cN).
• the melt flow index (MFR) measured at 230 ° C. is a value measured in accordance with JIS-K7210 (1999) at a load of 21.18 N (unit: g / 10 minutes).
• the branched polypropylene (H) is not particularly limited as long as the above formula is satisfied, but the melt flow index (MFR) is 1 to 20 g / 10 min from the viewpoint of film formability. Those within the range are preferable, and those within the range of 1 to 10 g / 10 min are more preferable.
• the melt tension is preferably in the range of 1 to 30 cN, more preferably in the range of 2 to 20 cN. When the melt tension is small, the uniformity of the height or density of the protrusions is inferior, and the uniformity of the film interlayer gap when used as a capacitor tends to be inferior. The higher the melt tension, the higher the uniformity of the height and density of the protrusions, the more likely the surface formation is dense (the number of protrusions per unit area increases, the number of small protrusions increases), and the film interlayer gap becomes uniform.
• a branched polypropylene (H) satisfying the relational expression that the melt tension (MS) and the melt flow index (MFR) measured at 230 ° C. are log (MS)> ⁇ 0.56 log (MFR) +0.74 is obtained.
• a method of mixing an oligomer or polymer having a branched structure and linear polypropylene The mixing may be performed by mixing pellets or by mixing and melting and kneading the pellets.
• transducing a long chain branched structure into a polypropylene molecule can also be used.
• independent granular protrusions can be formed by a method of orienting a sheet containing a different polymer such as polyethylene. Further, it contains branched polypropylene (H) satisfying the relational expression that melt tension (MS) and melt flow index (MFR) satisfy log (MS)> ⁇ 0.56 log (MFR) +0.74 at 230 ° C.
• H branched polypropylene
• the biaxially oriented polypropylene film has a finer surface, fewer coarse protrusions, and excellent uniformity of protrusions than the biaxially oriented polypropylene film obtained by blending different polymers such as polyethylene. Have.
• the size of the spherulite produced in the cooling process of the melt-extruded resin sheet can be easily controlled to be small, and the insulation produced in the stretching process It is possible to obtain a polypropylene film that suppresses generation of defects and has excellent voltage resistance.
• the branched polypropylene (H) has an action as an ⁇ crystal nucleating agent.
• the addition amount is within a certain range, it is possible to form a rough surface by crystal transformation.
• the crater size described later can be made small and dense, excellent in the uniformity of the density of the projections, and few coarse projections A biaxially oriented polypropylene film having excellent surface roughness can be obtained.
• the branched polypropylene (H) is preferably contained in the polypropylene resin in an amount of 0.5 to 8% by mass, and particularly preferably 1 to 5% by mass, whereby the winding property and voltage resistance are further improved.
• a film excellent in device processability and capacitor characteristics can be obtained.
• at least two melting peaks observed when measured by 2nd-Run appear in the polypropylene resin constituting the film. That is, it has a shoulder peak (148 to 157 ° C.) in addition to the first melting peak (temperature 160 to 172 ° C.).
• a shoulder peak 148 to 157 ° C.
• the first melting peak temperature 160 to 172 ° C.
• the branched polypropylene (H) preferably has 1 to 5 internal 3-substituted olefin structures per 10,000 carbon atoms.
• the presence of the internal tri-substituted olefin can be confirmed from the integral ratio of the signal in the region of 5.0 to 5.2 ppm and the signal of 0.5 to 2.0 ppm in the 1 H-NMR spectrum.
• Specific examples of the branched polypropylene (H) include “Profax PF-814” manufactured by Basell, and “Daploy HMS-PP” (WB130HMS, WB135HMS, etc.) manufactured by Borealis. Is preferably used since the gel component in the resin is small.
• melt crystallization temperature of PP is usually in the vicinity of 110 ° C., but rises to a range of 115 to 130 ° C. is there. Thereby, since crystallinity increases, the dimensional stability of the film under high temperature will increase.
• a method using crystal transformation is suitable. This method is preferably used compared to a method of adding particles such as resin, inorganic particles, and organic particles that are incompatible with polypropylene. This is because the number of substances that deteriorate the electrical characteristics is reduced, and the possibility of deteriorating electrical characteristics such as a dielectric breakdown voltage is low.
• the surface form obtained by crystal transformation will be described.
• the surface formation method by crystal transformation is the surface formation using two crystal systems of polypropylene described in the literature (M. Fujiyama et. Al., Journal of Applied Polymer Science 36, P.985-1048 (1988)).
• ⁇ crystal monoclinic system, crystal density 0.936 g / cm 3
• ⁇ crystal hexagonal system, crystal density 0.922 g / cm 3
• irregularities are formed on the film surface by transforming thermally unstable ⁇ crystals into ⁇ crystals in the stretching process.
• the aspect ratio of the circular protrusion changes corresponding to the ratio of the stretching ratio in the aspect ratio when the stretching is performed.
• the aspect ratio of the stretching ratio is 1, that is, the isotropic stretching is almost circular, and the aspect ratio is large.
• the protrusions are flattened, and the shape obtained by the sequential biaxial stretching method usually has a long axis in the transverse direction of the film (the width direction of the film roll).
• a plurality of craters having different shapes are overlapped, and the crater is closed in an annular shape so that it does not have a circular shape but may have an arcuate or semicircular shape.
• One method of generating protrusions is to increase the nucleation ability by adding a raw material having a nucleating agent effect. As a result, the number of nuclei increases, resulting in a large number of small fine protrusions. As a result, there can be obtained a surface on which protrusions are uniformly formed with few relatively flat portions.
• the raw material having the nucleating agent effect include the above-described branched polypropylene (H). By controlling the amount of the branched polypropylene (H) added and the film forming conditions, the shape of the protrusion can be controlled. As a result, a moderately roughened surface can be generated. .
• the biaxially oriented polypropylene film of the present invention has high dimensional stability at high temperatures, so that the shape maintenance as a capacitor is stable. That is, even when the film is exposed to high temperatures, the dimensional change of the film is small, so that end face curl, wrinkles, and stress distortion during capacitor fabrication are reduced, and the withstand voltage is improved without deteriorating electrical characteristics.
• the capacitor ambient temperature is as high as 120 to 140 ° C.
• the expansion of the capacitor, the end face curl, or the instability of the film interlayer may occur. As a result, the electrical characteristics of the capacitor may deteriorate, and it may be difficult to recover the insulating property.
• one side is preferably subjected to corona discharge treatment in order to perform metal vapor deposition, and the other surface is preferably not subjected to corona discharge treatment.
• linear polypropylene that can be used for the biaxially oriented polypropylene film of the present invention
• the linear polypropylene is usually used for a capacitor, but preferably has a cold xylene soluble part (hereinafter CXS) of 7% by mass or less. If the amount of CXS is too large, the film formation stability may be inferior, and when producing a biaxially stretched film, voids may be formed in the film, resulting in dimensional stability and dielectric breakdown resistance. There is a case where the decrease in the resistance becomes large.
• CXS cold xylene soluble part
• CXS cold xylene soluble part
• CXS refers to a polypropylene component dissolved in xylene when polypropylene is completely dissolved in xylene and then precipitated at 20 ° C., and has low stereoregularity. It is considered that this is a component that is difficult to crystallize due to a low molecular weight. If such a component is contained in a large amount in the resin, the thermal dimensional stability of the film may be inferior, and the dielectric breakdown voltage at a high temperature may be lowered. Therefore, CXS is preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less.
• the mesopentad fraction of the linear polypropylene is preferably 95% or more, more preferably 95.5% or more from the viewpoint of heat shrinkage characteristics at high temperatures. It is an index showing the stereoregularity of mesopentad fraction polypropylene. This value can be measured by a nuclear magnetic resonance method (NMR method). A higher value means a higher crystallinity and a higher melting point, and is particularly preferable from the viewpoints of dimensional stability at high temperatures and dielectric breakdown voltage.
• NMR method nuclear magnetic resonance method
• a higher value means a higher crystallinity and a higher melting point, and is particularly preferable from the viewpoints of dimensional stability at high temperatures and dielectric breakdown voltage.
• the mesopentad fraction is too large, it works advantageously with respect to dimensional stability at high temperatures, but the orientation tends to be extremely lowered, and the stretchability tends to be poor, so that film formation tends to be difficult.
• the withstand voltage at room temperature tends to decrease.
• a method of washing polypropylene resin powder with an aliphatic hydrocarbon such as n-heptane and a method of polymerizing by appropriately selecting a catalyst or a promoter are preferably employed. Is done.
• the melt flow index (MFR) is more preferably 1 to 10 g / 10 minutes (230 ° C., 21.18 N load), particularly preferably 2 to 5 g / 10 minutes (230 ° C., 21.18 N).
• the range of (load) is preferable from the viewpoint of film forming property.
• a method of controlling the average molecular weight or the molecular weight distribution is employed.
• Such a linear polypropylene is mainly composed of a homopolymer of propylene, but may contain a copolymer component derived from other unsaturated hydrocarbons as long as the object of the present invention is not impaired.
• monomer components include ethylene, 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene, 4-methylpentene-1, 5-ethylhexene- Examples include 1,1-octene, 1-decene, 1-dodecene, vinylcyclohexene, styrene, allylbenzene, cyclopentene, norbornene, and 5-methyl-2-norbornene.
• the copolymerization amount or blend amount is preferably less than 1 mol% in terms of copolymerization amount and less than 30 mass% in terms of blend amount from the viewpoint of dielectric breakdown resistance and dimensional stability.
• additives such as a crystal nucleating agent, an antioxidant, a heat stabilizer, a slipping agent, an antistatic agent, and an antiblocking agent are added to the biaxially oriented polypropylene film of the present invention within a range that does not impair the object of the present invention.
• An agent, a filler, a viscosity modifier, an anti-coloring agent and the like can also be contained.
• These additives can be contained in polypropylene pellets.
• the type and amount of the antioxidant is a phenolic compound having steric hindrance, and at least one of them is preferably a high molecular weight type having a molecular weight of 500 or more.
• BHT 2,6-di-t-butyl-p-cresol
• 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene for example, “Irganox” (registered trademark) manufactured by BASF) 1330: molecular weight 775.2
• tetrakis [methylene-3 (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] methane for example, "Irganox” (registered trademark) 1010: molecular weight 1177.7 manufactured by BASF
• Irganox registered trademark
• the total content of these antioxidants is preferably in the range of 0.03 to 1.0 mass% with respect to the total amount of polypropylene. If the amount of the antioxidant is too small, the long-term heat resistance may be poor. If the amount of the antioxidant is too large, the capacitor element may be adversely affected by blocking at a high temperature due to bleeding out of these antioxidants.
• a more preferable content is 0.1 to 0.9% by mass, particularly preferably 0.2 to 0.8% by mass.
• the biaxially oriented film of the present invention can contain a crystal nucleating agent.
• the branched polypropylene (H) already has an ⁇ -crystal or ⁇ -crystal nucleating agent effect by itself.
• Other examples include ⁇ -nucleating agents (dibenzylidene sorbitols, sodium benzoate, etc.), ⁇ -nucleating agents (potassium 1,2-hydroxystearate, magnesium benzoate, N, N′-dicyclohexyl-2,6).
• -Amide compounds such as naphthalene dicarboxamide, quinanacridon compounds and the like).
• the addition of these crystal nucleating agents may make it difficult to obtain crystallinity and the accompanying thermal characteristics, dimensional stability, and surface roughness. May have adverse effects. Therefore, the content is preferably less than 0.1% by mass. Of course, if the object of the present invention is achieved, the crystal nucleus material may not be contained.
• the glossiness of the surface of the biaxially oriented polypropylene film of the present invention is preferably in the range of 120 to 145%, more preferably 125 to 140%, still more preferably 130 to 135%.
• Low gloss means that light scattering on the film surface is large. This means that the irregularities on the film surface are dense.
• the glossiness is too low, it means that the height of the protrusions or the number of protrusions is very large. As a result, the slipperiness between the film layers increases, and the dimensional stability at high temperatures as a capacitor tends to decrease. Become.
• the ash content of the biaxially oriented polypropylene film of the present invention is preferably 50 ppm or less (mass basis, the same applies hereinafter), more preferably 30 ppm or less, and particularly preferably 20 ppm or less.
• the ash content is too large, the dielectric breakdown resistance of the film is lowered, and the dielectric breakdown strength may be lowered when a capacitor is used.
• contamination from the extrusion system during film formation should be reduced as much as possible. For example, it is possible to employ a method in which the bleed time is taken for 1 hour or longer and the path is sufficiently washed with a polymer before actually starting film formation.
• the type of capacitor that can use the biaxially oriented polypropylene film of the present invention is not limited. Specifically, from the viewpoint of electrode configuration, either a foil wound capacitor or a metal-deposited film capacitor may be used, and it is also preferable for an oil immersion type capacitor impregnated with insulating oil or a dry type capacitor not using insulating oil at all. Used. From the viewpoint of the shape, it may be a wound type or a laminated type. Among these, the metal vapor deposition film capacitor is particularly preferably used because of the characteristics of the film of the present invention.
• a polypropylene film since a polypropylene film usually has a low surface wetting tension and it is difficult to stably deposit metal, it is preferable to perform a surface treatment on the film in advance for the purpose of increasing the adhesion of the metal.
• the surface treatment include corona discharge treatment, plasma treatment, glow treatment, and flame treatment.
• the surface wetting tension of a polypropylene film is about 30 mN / m, but it is preferable that the wetting tension is about 37 to 50 mN / m, preferably about 39 to 48 mN / m by these surface treatments. Within this range of surface wetting tension, the adhesion to the metal film is excellent, and the security is good.
• the biaxially oriented polypropylene film of the present invention is obtained by melt-extruding, forming into a sheet, and biaxially stretching using the raw materials that can give the above-described characteristics.
• the biaxial stretching method can be obtained by any of the simultaneous inflation biaxial stretching method, the tenter simultaneous biaxial stretching method, and the tenter sequential biaxial stretching method, and among them, the stability of the stretching process and the thickness of the obtained film. It is preferable to employ a tenter sequential biaxial stretching method in terms of controlling the uniformity of the film and the surface shape of the film.
• a polypropylene resin A mixture of linear polypropylene and high melt tension polypropylene (branched polypropylene (H)) is preferable.
• polypropylene resin is melt-extruded and passed through a filtration filter, it is extruded from a slit die at a temperature of 230 to 260 ° C. And solidify on a cooling drum to obtain an unstretched sheet.
• the resin in order to efficiently generate ⁇ crystals, it is preferable to maintain the resin for a predetermined time at a temperature at which the ⁇ crystal generation efficiency is maximized, and this temperature is usually 115 to 135 ° C.
• the holding time is preferably 1 second or longer.
• the process can be appropriately determined according to the resin temperature, the extrusion amount, the take-up speed, and the like.
• the diameter of the cooling drum greatly affects the holding time, the diameter of the drum is preferably at least 1 m.
• the cooling drum temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and further 85 ° C. or higher.
• this temperature is 120 degrees C or less, Furthermore, 110 degrees C or less, Furthermore, it is 100 degrees C or less. If the casting drum temperature is too high, the crystallization of the film will proceed excessively, making it difficult to stretch in the subsequent process, and voids may be formed in the film, resulting in a decrease in dielectric breakdown resistance.
• any method of electrostatic application method, adhesion method using surface tension of water, air knife method, press roll method, underwater casting method, etc. can be used. It may be used.
• the air knife method is preferable because it has good flatness and can control the heat shrinkage characteristics and surface roughness of the front and back surfaces.
• the air temperature of the air knife is preferably 35 ° C. or higher, more preferably 40 ° C. or higher, and further 45 ° C. or higher.
• the temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 100 ° C. or lower. If the air temperature of the air knife is too high, crystallization of the film proceeds too much, and stretching in the subsequent process may be difficult, voids may be formed in the film, and the dielectric breakdown resistance may be degraded. On the other hand, if the air temperature of the air knife is too low, crystal formation may be insufficient, and it may be difficult to obtain the desired heat shrinkage stress and surface roughness.
• the air knife blown air speed is preferably 130 to 150 m / s, and preferably has a double-pipe structure in order to improve the uniformity in the width direction. If the air speed is too low, sufficient adhesion with the cast drum cannot be imparted and the film-forming property is lowered, and if it is too large, adhesion to the uniform casting drum cannot be performed, film-forming property, uneven quality, Detrimental effects such as uneven thickness are likely to occur. In order to prevent vibration of the film, it is preferable to adjust the position of the air knife so that air flows downstream of the film formation.
• this unstretched sheet is biaxially stretched to be biaxially oriented.
• the unstretched film is preheated through a roll maintained at 120 to 150 ° C., and then the sheet is maintained at a temperature of 130 ° C. to 150 ° C. In this case, after stretching by 4 to 7 times as a stretching ratio in the longitudinal direction. Cool to room temperature.
• the stretching method and the stretching ratio are not particularly limited and are appropriately selected depending on the polymer characteristics to be used.
• the stretched film is continuously guided to a tenter, stretched 7 to 15 times in the width direction at a temperature of 140 to 165 ° C., and then given a relaxation of 20 to 30% in the width direction, and a temperature of 140 to 165 ° C. After heat setting with, cool at 100-150 ° C. Particularly preferred is a relaxation rate of 22 to 28%, and more preferred is a relaxation rate of 22 to 25%.
• each of the relaxing steps provided in a plurality of stages is hereinafter referred to as “relaxing process (II)”.
• the first stage of the relaxing process (II) has the highest relaxation rate.
• the relaxing step (II) is preferably three or more steps.
• the relaxation process (II) is performed in the heat fixing chamber.
• the overall relaxation rate (hereinafter referred to as “total relaxation rate”) is determined by the first heat fixing chamber inlet width (A) and the last heat fixing chamber outlet. Using the width (B), the definition is as follows.
• Total relaxation rate (%) final heat fixing chamber outlet width (B) / first heat fixing chamber inlet width (A) ⁇ 100 When the total relaxation rate is set to 20%, the following relaxation rates can be taken. Often, the sum of the relaxation rates at each stage is greater than the total relaxation rate.
• Room 1 1st stage relaxation rate 10.0% Room 2 Second stage relaxation rate 8.0% Room 3 Third stage relaxation rate 3.4%.
• the desired heat-absorbing stress value can be stably obtained by inclining the temperature and magnification. Further, by performing relaxation also in the cooling zone, it becomes possible to further control the heat absorption stress value.
• the film is relaxed in the tenter, and after the film comes out of the tenter, the film is rapidly cooled at room temperature for 3 seconds or more before the film is wound, thereby further improving the dimensional stability of the film. Particularly preferably, it is 5 seconds or more. If the rapid cooling time at room temperature is shorter than 3 seconds, the film is wound before the dimensions of the film are fixed. Therefore, after unwinding the film, the dimensions of the film change and it is difficult to obtain the target heat shrinkage stress value.
• a method of rapidly cooling the film at room temperature it is preferable to blow air or to control the temperature of the film transport roll to room temperature.
• a metal film can be provided on the surface of the biaxially oriented polypropylene film of the present invention to form a metallized film.
• the method is not particularly limited, but, for example, a method of depositing a metal film such as an aluminum vapor deposition film to be an internal electrode of a film capacitor by depositing aluminum on at least one side of a polypropylene film is preferably used.
• a metal film such as an aluminum vapor deposition film to be an internal electrode of a film capacitor by depositing aluminum on at least one side of a polypropylene film is preferably used.
• other metal components such as nickel, copper, gold, silver, chromium and zinc can be deposited simultaneously or sequentially with aluminum.
• a protective layer can be provided on the deposited film with oil or the like.
• the thickness of the metal film is preferably in the range of 20 to 100 nm from the viewpoint of electrical characteristics and self-heeling properties of the film capacitor.
• the surface electrical resistance value of the metal film is preferably in the range of 1 to 20 ⁇ / ⁇ .
• the surface electrical resistance value can be controlled by the type of metal used and the film thickness. The method for measuring the surface electrical resistance value will be described later.
• the metallized film can be subjected to an aging treatment at a specific temperature or a heat treatment. Also, a coating such as polyphenylene oxide can be applied to at least one side of the metallized film for insulation or other purposes.
• the metallized film thus obtained can be laminated or rolled by various methods to obtain a film capacitor.
• An example of a preferred method for producing a wound film capacitor is as follows.
• Aluminum is vacuum-deposited on one side of a polypropylene film to produce a metallized polypropylene film. At that time, aluminum is vapor-deposited so that a striped margin portion (non-deposition portion) is generated in the longitudinal direction of the film.
• a tape-shaped take-up reel having a margin portion continuous in the longitudinal direction at one end in the width direction is formed by inserting a blade into the center of each vapor deposition portion and the center of each margin portion on the surface.
• a two-leaf metallized polypropylene film is drawn out from a take-up reel having a margin part on the left side in the width direction and a take-up reel having a margin part on the right side. Get a round body.
• a metallized propylene film in which the margin part is on the left in the width direction and the deposited metal is present to the right, and a metallized polypropylene film in which the margin part is on the right in the width direction and the deposited metal is present to the left The layers are stacked alternately.
• the core is removed from this wound body, the wound body is pressed, metallized on both ends in the width direction is sprayed to form an external electrode, and a lead wire is welded to the metallized to obtain a wound type film capacitor. .
• Film capacitors are used in a wide variety of applications such as for railway vehicles, for general household appliances (for example, for TVs and refrigerators), for automobiles (including hybrid cars, electric cars, etc.), for wind power generation and for solar power generation.
• the film capacitor of the present invention can also be suitably used for these applications.
• the characteristic value measurement method and evaluation method in the present invention are as follows. *
• Heat shrinkage rate (%) ((L0-L1) / L0) ⁇ 100.
• WMV is the mass method thickness (unit: mm) of the film determined according to JIS-C2330 (2001) 7.4.1.2. The measurement was performed 3 times and the average was obtained.
• Melt flow index (MFR) According to JIS-K7210 (1999), measurement was performed at a measurement temperature of 230 ° C. and a load of 21.18 N.
• Melt tension (MS) Measurement was performed using an apparatus for MFR measurement described in JIS-K7210 (1999). Using a melt tension tester manufactured by Toyo Seiki Seisakusho Co., Ltd., the polypropylene is heated to 230 ° C., the molten polypropylene is discharged at an extrusion speed of 15 mm / min to form a strand, and the tension when the strand is taken up at a speed of 6.5 m / min. was measured as melt tension.
• Peak splitting was performed using WINFIT software (Bruker). At that time, the peak area is divided from the peak area on the high magnetic field side as follows, and the attached software is automatically fitted to optimize the peak area division, and then mmmm and ss (mmmm spinning) The sum of the peak fractions of the sideband peaks was defined as the mesopentad fraction (mmmm). The measurement was performed 5 times, and the average value was defined as the mesopentad fraction.
• Measurement conditions Apparatus: ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. Measurement nucleus: 1 H nucleus (resonance frequency: 500 MHz) Measurement concentration: 2% by mass Solvent: Heavy orthodichlorobenzene Measurement temperature: 120 ° C Pulse width: 45 ° Pulse repetition time: 7 seconds Conversion count: 512 times Measurement mode: non decoupling B.
• a blade was put in the center of each vapor deposition section and the center of each margin section and slit, and a take-up reel was formed into a tape having a width of 20 mm and a margin of 0.5 mm on the left or right. Two pieces of each of the left and right margins of the obtained reel are overlapped and rolled so that the vapor deposition part protrudes 0.5 mm from the margin part in the width direction, and a round element having a capacitance of about 10 ⁇ F Got. KAW-4NHB manufactured by Minato Co., Ltd. was used for element winding. After aging in a reduced-pressure atmosphere at 140 ° C.
• element winding yield The ratio of the number of rejected products to the total number of manufactured products was expressed as a percentage and used as an index of workability (hereinafter this ratio is referred to as “element winding yield”). The higher the element winding yield, the better. 95% or more was designated as “A”, less than 95% as 80% or more as “B”, and less than 80% as “C”. The production number was evaluated with 50 elements.
• the capacitor element was wound with an element winding machine (KAW-4NHB) manufactured by Minato Seisakusho Co., Ltd., metallized, and then heat-treated at 140 ° C. for 10 hours under reduced pressure. A capacitor element was finished by mounting. The capacitance of the capacitor element at this time was 10 ⁇ F.
• KAW-4NHB element winding machine manufactured by Minato Seisakusho Co., Ltd.
• the number of manufactured products was evaluated using 10 elements, and expressed as an average value.
• ⁇ C / C (%) ((C1-C0) / C0) ⁇ 100.
• Example 1 As a linear polypropylene, a branched polypropylene produced by Basell Co., Ltd. was added to 100 parts by mass of a polypropylene polymer manufactured by Prime Polymer Co., Ltd. having a mesopentad fraction of 97.9% and a melt mass flow rate (MFR) of 2.6 g / 10 min. 0.5 parts by mass of resin (high melt tension polypropylene Profax PF-814 meso pentad fraction 91.0%) is blended and supplied to an extruder at a temperature of 250 ° C., and in sheet form from a T-type slit die at a resin temperature of 250 ° C.
• MFR melt mass flow rate
• the molten sheet was melt-extruded and cooled and solidified on a casting drum having a diameter of 1 m held at 90 ° C. at an air knife temperature of 90 ° C. and an air speed of 140 m / s.
• the retention time at 110 to 135 ° C. was 2.8 seconds as a result of measurement with a radiation thermometer.
• the sheet was gradually preheated to 140 ° C., then kept at a temperature of 145 ° C., passed between rolls provided with a difference in peripheral speed, and stretched 4.8 times in the longitudinal direction. At that time, a stretching heater (output 3.5 kW) was used in the stretching section to supplement the amount of heat and stretching.
• the film was guided to a tenter, stretched 10 times in the width direction at a stretching temperature of 160 ° C., and then relaxed in three stages with a relaxation rate of 23% in total in the width direction. (The first stage is 12.0%, the second stage is 9.0%, and the third stage is 3.9%.)
• Heat treatment is performed at a heat setting temperature of 150 ° C. and a cooling temperature of 140 ° C., and then at room temperature.
• the film was quenched for 5 seconds to obtain a biaxially oriented polypropylene film having a film thickness of 3.0 ⁇ m.
• a corona discharge treatment was performed on the surface on one side in the air with a treatment strength of 25 W ⁇ min / m 2 .
• the properties of the biaxially oriented polypropylene film thus obtained were as shown in Tables 1 and 2. Both withstand voltage and device processability were excellent.
• Example 2 A biaxially oriented polypropylene film was obtained in the same manner as in Example 1 except that the mesopentad fraction of the linear polypropylene was 95.1%. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 3 A biaxially oriented polypropylene film was obtained in the same manner as in Example 1 except that the film thickness was 1 ⁇ m, the tenter stretching temperature was 145 ° C., the heat setting temperature was 142 ° C., and the cooling temperature was 125 ° C.
• the characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 4 The linear polypropylene has a mesopentad fraction of 97.4%, a film thickness of 2.5 ⁇ m, and a total relaxation rate of 25% (first stage 12.5%, second stage 9.0%, third stage 5.8). %), A film was formed in the same manner as in Example 1 to obtain a biaxially oriented polypropylene film. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 5 The linear polypropylene has a mesopentad fraction of 97.4%, a film thickness of 2.5 ⁇ m, and a total relaxation rate of 22% (first stage 11.0%, second stage 8.0%, third stage 4.7). %), A film was formed in the same manner as in Example 1 to obtain a biaxially oriented polypropylene film. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 6 Tenter stretching temperature 165 ° C, heat setting temperature 165 ° C, cooling temperature 150 ° C, total relaxation rate 28% (1st stage 14.0%, second stage 11.0%, third stage 5.9% Except that the film was formed in the same manner as in Example 1 to obtain a biaxially oriented polypropylene film.
• the characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• the linear polypropylene has a mesopentad fraction of 95.1%, a tenter stretching temperature of 140 ° C, a heat setting temperature of 140 ° C, a cooling temperature of 100 ° C, and a total relaxation rate of 20% (1st stage 10.0% The second stage was 8.0%, the third stage was 3.4%), and a film was formed in the same manner as in Example 1 except that the room temperature cooling time was 3 seconds to obtain a biaxially oriented polypropylene film.
• the characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 8 A biaxially oriented polypropylene film was obtained in the same manner as in Example 1 except that the mesopentad fraction of the linear polypropylene was 97.4%. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 9 The film thickness is 2 ⁇ m, the stretching temperature at the tenter is 140 ° C., the heat setting temperature is 140 ° C., the cooling temperature is 100 ° C., and the total relaxation rate is 20% (first stage 11.0%, second stage 7.0%, Film formation was performed in the same manner as in Example 1 except that the third stage (3.3%) and the room temperature cooling time were set to 3 seconds to obtain a biaxially oriented polypropylene film.
• the characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 1 A biaxially oriented polypropylene film was obtained in the same manner as in Example 1 except that the mesopentad fraction of the linear polypropylene was 98.5%. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 2 A biaxially oriented polypropylene film was obtained in the same manner as in Example 1 except that the mesopentad fraction of the linear polypropylene was 94.5%. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• the linear polypropylene has a mesopentad fraction of 97.5%, a total relaxation rate of 15% (1st stage 8.0%, 2nd stage 5.0%, 3rd stage 2.7%), room temperature quenching time Except for 2.5 seconds, a film was formed in the same manner as in Example 1 to obtain a biaxially oriented polypropylene film.
• the characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Linear polypropylene has a mesopentad fraction of 98.5%, a cooling temperature of 50 ° C., and a relaxation rate of 15% (first stage 5.0%, second stage 5.3%, third stage 5.6%). Except for the above, a film was formed in the same manner as in Example 1 to obtain a biaxially oriented polypropylene film. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 5 The film thickness was 5 ⁇ m, the stretching temperature was 165 ° C., the heat setting temperature was 165 ° C., and the relaxation rate was 28% (first stage 9.3%, second stage 10.3%, third stage 11.5%). Except for the above, film formation was carried out in the same manner as in Example 1 to obtain a biaxially oriented polypropylene film. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• the linear polypropylene has a mesopentad fraction of 94.5%, a stretching temperature of 165 ° C., a heat setting temperature of 165 ° C., and a relaxation rate of 25% (first stage 13.0%, second stage 9.0%, second stage A biaxially oriented polypropylene film was obtained in the same manner as in Example 1 except that the three steps were 5.2%.
• the characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.
• Example 8 Film formation was performed in the same manner as in Example 1 except that the mesopentad fraction of linear polypropylene was 94.5%, the stretching temperature was 140 ° C, the heat setting temperature was 140 ° C, the cooling temperature was 100 ° C, and the film thickness was 5 ⁇ m. And a biaxially oriented polypropylene film was obtained. The characteristics of the obtained biaxially oriented polypropylene film are shown in Tables 1 and 2.

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